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Title: Combining STM, RAIRS and TPD to Decipher the Dispersion and Interactions Between Active Sites in RhCu Single-Atom Alloys

Journal Article · · ChemCatChem

Abstract Single‐atom alloys are a new class of heterogeneous catalyst in which trace amounts of metal dopants exist as individual, isolated sites in a host metal. In this study, we examine RhCu, a new single‐atom alloy with a combination of scanning tunneling microscopy, reflectance absorption infrared spectroscopy, and temperature programed desorption to understand the atomic structure of the alloy and correlate this with the behavior of CO, a common probe molecule. We find that Rh alloys into Cu(111) preferentially from step edges. As such, step density plays an important role in the vibrational structure of CO on isolated Rh sites. We find that atomically dispersed Rh sites can be close enough together to have dipole‐dipole coupling interactions. Together, this combined experimental approach enables us to understand the alloying mechanism of Rh with Cu and yields important signatures of the atomic sites that are useful in benchmarking CO vibrational data.

Research Organization:
Tufts Univ., Medford, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0004738; FG02-10ER16170
OSTI ID:
1595290
Alternate ID(s):
OSTI ID: 1573523; OSTI ID: 1773871
Journal Information:
ChemCatChem, Vol. 12, Issue 2; ISSN 1867-3880
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

References (52)

Thermal desorption of gases journal July 1962
Correlation between surface stress and the vibrational shift of CO chemisorbed on Cu surfaces journal August 1994
Lonely Atoms with Special Gifts: Breaking Linear Scaling Relationships in Heterogeneous Catalysis with Single-Atom Alloys journal September 2018
Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture) journal April 2008
Homogeneity of Surface Sites in Supported Single-Site Metal Catalysts: Assessment with Band Widths of Metal Carbonyl Infrared Spectra journal September 2016
Tackling CO Poisoning with Single-Atom Alloy Catalysts journal May 2016
Importance of Kinetics in Surface Alloying: A Comparison of the Diffusion Pathways of Pd and Ag Atoms on Cu(111) journal June 2009
Breaking the scaling relationship via thermally stable Pt/Cu single atom alloys for catalytic dehydrogenation journal October 2018
Growth of Rh, Pd, and Pt films on Cu(100) journal February 1990
The influence of surface defects on the infrared spectra of adsorbed species journal January 1992
CO/Rh(111): Vibrational frequency shifts and lateral interactions in adsorbate layers journal November 2001
Surface free energies of solid metals: Estimation from liquid surface tension measurements journal January 1977
Toward Effective Utilization of Methane: Machine Learning Prediction of Adsorption Energies on Metal Alloys journal March 2018
Theoretical Study of the Catalytic Activity of Bimetallic RhCu Surfaces and Nanoparticles toward H 2 Dissociation journal August 2002
Structure–activity relationships in supported Au catalysts journal January 2006
Effects of ensembles, ligand, and strain on adsorbate binding to alloy surfaces journal November 2018
Size and Shape Control of Metal Nanoparticles for Reaction Selectivity in Catalysis journal August 2012
On the structure of CO adlayers on Cu(100) and Cu(111) journal January 1979
Effect of Substrate Strain on Adsorption journal May 1998
FEATURES AND CATALYTIC PROPERTIES OF RhCu : A REVIEW journal October 2010
Elucidating the Stability and Reactivity of Surface Intermediates on Single-Atom Alloy Catalysts journal April 2018
Surface restructuring of Cu-based single-atom alloy catalysts under reaction conditions: the essential role of adsorbates journal January 2017
Initial Oxidation of Cu( hkl ) Surfaces Vicinal to Cu(111): A High-Throughput Study of Structure Sensitivity journal July 2012
CO adsorption studies on a stepped Cu(111) surface journal July 1994
Atomically Dispersed Supported Metal Catalysts: Seeing Is Believing journal April 2019
H 2 Activation and Spillover on Catalytically Relevant Pt–Cu Single Atom Alloys journal August 2015
Carbon Monoxide Poisoning Resistance and Structural Stability of Single Atom Alloys journal January 2018
Selectivity for ethanol partial oxidation: the unique chemistry of single-atom alloy catalysts on Au, Ag, and Cu(111) journal January 2019
Theoretical Study of Methanol Synthesis from CO 2 Hydrogenation on Metal-Doped Cu(111) Surfaces journal December 2011
Dipole coupling and chemical shifts in IRAS of CO adsorbed on Cu(110) journal December 1982
Methane Dehydrogenation on Rh@Cu(111):  A First-Principles Study of a Model Catalyst journal September 2006
The chemisorption of CO and CO2 on Rh(111) studied by high resolution electron energy loss spectroscopy journal January 1980
Activities and immiscibility in the system Cu-Rh journal July 2000
Adsorption of Rh, Pd, Ir, and Pt on the Au(111) and Cu(111) Surfaces: A Density Functional Theory Investigation journal August 2014
Investigating the Reactivity of Single Atom Alloys Using Density Functional Theory journal January 2018
CH4 dehydrogenation on Cu(111), Cu@Cu(111), Rh@Cu(111) and RhCu(111) surfaces: A comparison studies of catalytic activity journal June 2015
Catalytic Activity of Single Transition-Metal Atom Doped in Cu(111) Surface for Heterogeneous Hydrogenation journal July 2013
Atomic-Scale Imaging and Electronic Structure Determination of Catalytic Sites on Pd/Cu Near Surface Alloys journal March 2009
Atomic Scale Surface Structure of Pt/Cu(111) Surface Alloys journal January 2014
Alloy catalysts: the concepts journal December 2001
The Cu−Rh (Copper-Rhodium) system journal March 1982
Single-Atom Alloys as a Reductionist Approach to the Rational Design of Heterogeneous Catalysts journal December 2018
Catalytic sites are finally in sight journal June 2019
Frequency shifts in the spectra of molecules adsorbed on metals, with emphasis on the infrared spectrum of adsorbed CO journal December 1978
Promoter and poisoning effects on NO-catalyzed dissociation on bimetallic RhCu(111) surfaces journal April 2006
Vibrational spectroscopy of CO adsorbed on supported ultra-small transition metal particles and single metal atoms journal May 2000
Preparation, Characterization, and Activity forn-Hexane Reactions of Alumina-Supported Rhodium–Copper Catalysts journal October 1997
Free-atom-like d states in single-atom alloy catalysts journal August 2018
Theoretical Study of CO and NO Chemisorption on RhCu(111) Surfaces journal March 2005
Formation of Pt and Rh Nanoclusters on a Graphene Moiré Pattern on Cu(111) journal October 2015
Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation journal January 2018
FT-rairs, eels and leed studies of the adsorption of carbon monoxide on Cu(111) journal September 1988